Extraction of rhodium from supported liquid-phase hydroformylation catalysts with supercritical carbon dioxide

Abstract

The continuous extraction of the rhodium inventory in supported liquid-phase (SLP) catalytic materials utilized in the hydroformylation (HyFo) of 1-butene was investigated by supercritical carbon dioxide (scCO₂). Optimization of extraction efficiency involved varying parameters such as temperature (90 and 120 °C), pressure (10, 20 and 30 MPa), and the addition of methanol as a polar co-feed to the extraction medium (0–20 vol%). The results underscored the critical role of methanol in facilitating extraction, as experiments employing pure scCO₂ yielded no rhodium recovery. Furthermore, extraction performance demonstrated sensitivity to temperature and pressure adjustments during the process. Notably, the use of 10 vol% methanol at 120 °C and 30 MPa achieved complete rhodium extraction from the grained SLP materials, which was identified as the optimum extraction condition. This study highlights the potential for scaling up in-situ rhodium extraction processes within HyFo production plants based on SLP catalysts, emphasizing significant implications for industrial applications.